| 164019-41-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 164019-41-4
• 化学式: C₄₉H₄₀O₂P₂Pd
• 分子量: 829.223
• InChiKey: RBZWFGIJHVFNDF-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  、 一氧化碳 以 氘代苯 为溶剂， 生成 trans-[PhCOPd(PhCOO)(PPh3)2]
  参考文献：
  名称：

  Indirect Formation of Carboxylic Acids via Anhydrides in the Palladium-Catalyzed Hydroxycarbonylation of Aromatic Halides

  摘要：

  The carbonylation of [(Ph(3)P)(2)Pd(2)Ph(2)(mu-OH)(2)] (2) in the presence of PhI results in the quantitative formation of benzoic anhydride and [(Ph(3)P)(2)Pd-2(PhCO)(2)(mu-I)(2)] (3). This transformation contributes to some extent to the production of benzoic acid from haloarenes, CO, and alkali, catalyzed by [(Ph(3)P)(2)PdCl2], the latter being converted to 2 under the reaction conditions. Phenyl- and benzoylpalladium benzoates are likely key intermediates in the indirect formation of the acid, via the anhydride, by the carbonylation of 2. One such complex, [L(2)Pd(Ph)(PhCOO)] (5, L Cy(3)P), was isolated from the carbonylation of [(Cy(3)P)(2)Pd(2)Ph(2)(mu-OH)(2)] (4) in hexane. The related complexes, [L(2)Pd(2)Ph(2)(mu-PhCOO)(2)] (6, L = PPh(3); 7, L = PCy(3)), were prepared from benzoic acid and hydroxo complexes 2 and 4, respectively. Treatment of 6 and 7 with the corresponding phosphine afforded [L(2)pd(ph)(phCOO)] (8, L = PPh(3); 5, L = PCy(3)). When 6-8 were reacted with CO in benzene, benzoic anhydride was readily formed, whereas in the case of 5 both carbonylation and reductive elimination were sluggish. Crystallographic data for 6 (1:2 chloroform solvate): space group Peen, a = 22.499(4) Angstrom, b = 10.992(3) Angstrom, c = 24.514(6) Angstrom, V = 6062.4(23) Angstrom(3), Z = 4, R = 0.056, and R(w) = 0.038.

  DOI：

  10.1021/ja00120a012
• 作为产物：
  描述：

  trans-[PhCOPd(PhCOO)(PPh3)2] 以 further solvent(s) 为溶剂， 生成
  参考文献：
  名称：

  涉及钯活化的碳-卤素键和碳-氧键的氧化加成步骤

  摘要：

  通过 原位 31 P NMR光谱研究了涉及通过钯激活碳-卤素和碳-氧键的Heck反应的不同修饰（用碘代苯或苯甲酸酐进行苯乙烯苯基化和碘代苯羰基化，还原偶联和还原） 。反应的催化循环包括氧化成 原位 形成的Pd（0） 。该步骤中的产物组成很大程度上取决于反应混合物的组成，这与主要催化过程中的PhX转化率以及催化剂前体的性质有关。提出了关于在膦配体存在下烯烃芳基化中催化循环机理的新假设。该假设与NMR监测数据和动力学同位素效应的值一致。

  DOI：

  10.1007/s10975-005-0101-0

文献信息

• ——
  作者：A. F. Shmidt、V. V. Smirnov

  DOI：10.1023/a:1015364310409

  日期：——

  The main steps of the catalytic cycle of the alkene arylation reaction with the participation of anhydrides of aromatic acids as arylation agents were studied by P-31 NMR spectroscopy. In contrast to the mechanism proposed earlier, palladium complexes containing benzoate anions as acidoligands were not found in the reaction mixture. It was found that the catalytic cycle of the reaction includes the steps of oxidative addition of Pd(0) formed in situ to the anhydride of acid, the substitution of acidoligand, and the elimination of the CO molecule. Further transformations probably take place according to the usual steps of the Heck reaction. It was shown that CO elimination is a limiting step.